Process for producing propargylcarbinol compounds

ABSTRACT

The present invention provides a process for producing a propargylcarbinol compound of formula (I): ##STR1## wherein R 1  and R 2  are as defined herein. The process comprises reacting a haloallylcarbinol compound of formula (II) with a base. The present invention also relates to a process for producing the haloallylcarbinol compound. The above propargylcarbinol compound is useful as an intermediate for agrochemicals, pharmaceuticals, perfumes, resin monomers, and the like.

This application is a continuation of application Ser. No. 08/107,015,filed Aug. 17, 1993 abandoned; which in turn is a division ofapplication Ser. No. 07/538,555, filed Jun. 15, 1990, now U.S. Pat. No.5,258,529.

BACKGROUND OF THE INVENTION

1. Field of the Industry

The present invention relates to a process for producingpropargylcarbinols useful as intermediates for agrochemicals,pharmaceuticals, perfumes, resin monomers, and the like.

2. Description of Related Prior Art

Propargylcarbinols have been heretofore produced by a Grignard reactionof propargyl bromide or propargyl chloride and a ketone or aldehydecompound.

Since, however, propargyl bromide and propargyl chloride are detonableor capable of monopropellant-type burning, in view of safety, theinhibition of the detonability is required in the industrial bulk usethereof (Fire Technology, Vol. 5, p. 100, 1969, etc.).

Therefore, the above-mentioned process is not always an industriallyadvantageous one.

SUMMARY OF THE INVENTION

The present inventors have found a process for producing apropargylcarbinol by dehalogenation with a base through ahaloallylcarbinol, derived from a ketone compound or an aldehydecompound and 2,3-dihalo-1-propene, without using propargyl bromide orpropargyl chloride.

The present invention relates to a haloallylcarbinol-producing reaction(step 1) for producing a haloallylcarbinol compound of the formula (II)(sometimes referred to as haloallylcarbinol Compound II hereinafter)##STR2## where R¹ and R² independently represent a hydrogen atom; a C₁-C₁₅ alkyl group which may be substituted with at least one memberselected from the group consisting of halogen atoms, a hydroxyl group, aphenyl group, an phenoxy group, a phenyl or phenoxy group substitutedwith at least one member selected from the group consisting of halogenatoms and hydroxyl, alkoxy, phenoxy, dialkylamino and methylenedioxygroups, and aralkyloxy group, a dialkylamino group, an alkylthio group,a phenylthio group, a biphenyl group and a phenylalkyl group; a C₂ -C₁₅alkenyl group which may be substituted with at least one member selectedfrom the group consisting of halogen atoms, a hydroxyl group, a phenylgroup, a phenoxy group, a phenyl or phenoxy group substituted with atleast one member selected from the group consisting of halogen atoms andhydroxyl, alkoxy, phenoxy, dialkylamino and methylenedioxy groups, adialkylamino group, an alkylthio group, a phenylthio group, a biphenylgroup and a phenylalkyl group; a C₂ -C₁₅ alkynyl group which may besubstituted with at least one member selected from the group consistingof halogen atoms, a hydroxyl group, a phenyl group, a phenoxy group, aphenyl or phenoxy group substituted with at least one member selectedfrom the group consisting of halogen atoms and hydroxyl, alkoxy,phenoxy, dialkylamino and methylenedioxy groups, a dialkylamino group,an alkylthio group, a phenylthio group, a biphenyl group and aphenylalkyl group; a C₃ -C₁₅ cycloalkyl group; a C₄ -C₁₅ cycloalkenylgroup; or a phenyl, napthyl, furyl or thienyl group which may besubstituted with at least one member selected from the group consistingof halogen atoms, and hydroxyl, alkyl, alkoxy, phenoxy, dialkylamino andmethylenedioxy groups; or R¹ and R² together represent a C₂ -C₁₅alkylene or alkenylene chain; and X² represents a chlorine, bromine oriodine atom, with proviso that the carbon atoms in the 1-positions of R¹and R² do not together form tertiary carbon atoms and that when one ofR¹ and R² is the furyl group, the other does not represent a hydrogenatom: which comprises reacting

a carbonyl compound of the formula (III) (referred to as Compound (III)hereinafter) ##STR3## where R¹ and R² are as defined above, with

a dihalopropene compound of the formula (IV) (referred to as Compound(IV) hereinafter) ##STR4## where X¹ and X² independently represent achlorine, bromine or iodine atom in the presence of zinc and water.

Further, the present invention provides a process (step 2) for producinga propargylcarbinol compound (referred to as propargylcarbinol Compound(I) hereinafter) of the formula (I): ##STR5## where R¹ and R² are asdefined above, which comprises reacting haloallylcarbinol Compound (II)obtained in the above step 1 with a base.

An object of the present invention is to provide a process, with safetyand industrial advantage, for producing a propargylcarbinol compounduseful as an intermediate for an agrochemical, pharmaceutical, perfumeand resin monomer without using propargyl bromide or propargyl chloride.

PREFERRED EMBODIMENTS OF THE INVENTION

In the present invention, as preferred substituents R¹ and R², each ofR¹ and R² independently of the other represents a hydrogen atom, a C₁-C₁₅ alkyl group which may be substituted with at least one memberselected from the group consisting of halogen atoms and hydroxyl,phenyl, phenoxy, aralkyloxy, dialkylamino, alkylthio, phenylthio,biphenyl and phenylalkyl groups; a C₃ -C₉ cycloalkyl or cycloalkenylgroup; a C₂ -C₉ alkenyl group which may be substituted with a phenylgroup; a C₂ -C₆ alkynyl group; or a phenyl, napthyl, furyl or thienylgroup which may be substituted with at least one member selected fromthe group consisting of halogen atoms and hydroxyl, alkyl, alkyloxy,phenoxy, dialkylamino and methylenedioxy groups. And, as more preferredsubstituents, each of R¹ and R² independently of the other represents aC₁ -C₁₅ alkyl group which may be substituted with a phenyl a C₂ -C₉alkenyl group which may be substituted with a phenyl group; a C₅ -C₇cycloalkyl or cycloalkenyl group; a phenyl, naphthyl or thienyl groupwhich may be substituted with at least one member selected from thegroup consisting of halogen atoms, C₁ -C₃ alkyl, C₁ -C₃ alkoxy, phenoxyand methylenedioxy groups; or a hydrogen atom.

Each step of the present invention is detailed below.

Examples of Compound (III) used at the step 1 include C₁ -C₁₅ linearaliphatic aldehydes such as formaldehyde, acetaldehyde, propionaldehyde,propenal, butanal, pentanal, hexanal, heptanal, 6-heptynal, decanal,dodecanal, tetradecanal, hexadecanal, etc.; branched or cyclic aliphaticaldehydes such as 2-methylpropionaldehyde, 4-methyl-1-pentanal,2-methyl-2-pentenal, citral, cyclohexanecarbaldehyde, etc.;halogen-substituted aliphatic aldehydes such as 2-chlorohexanal,3-bromoheptanal, etc.; hydroxyl-substituted aliphatic aldehydes such as3-hydroxybutanal, 6-hydroxyhexanal, etc.; aryl-containing aliphaticaldehydes such as phenylacetaldehyde, 2-phenylpropionaldehyde,biphenylacetaldehyde, cinnamic aldehyde, phenylpropynal, etc.;N,N-dialkylamino, alkylthio, arylthio, alkyloxy or aryloxygroup-containing aliphatic aldehydes such as2-(N,N-dimethylamino)-propionaldehyde, 4-(N,N-diethylamino)-1-butanal,4-methylthio-1-butanal, 4-phenylthio-1-butanal, 6-methoxy-1-hexanal,benzyloxyacetaldehyde, 6-phenoxy-1-hexanal, etc.; aromatic aldehydessuch as benzaldehyde, o-tolaldehyde, m-tolaldehyde, p-tolaldehyde,p-methoxybenzaldehyde, 2,4-dimethoxybenzaldehyde, m-phenoxybenzaldehyde,p-chlorobenzaldehyde, o-bromobenzaldehyde, 2,4-dichlorobenzaldehyde,salicylaldehyde, 4-(N,N-dimethylamino)benzaldehyde, piperonal, etc.;thiophenecarbaldehydes such as 2-thiophenecarbaldehyde,3-thiophenecarbaldehyde, etc.; linear, branched or cyclic alkyl, alkenylor alkynyl-containing aliphatic ketones such as acetone, methyl ethylketone, methyl n-propyl ketone, methyl isopropyl ketone, methyl n-butylketone, methyl isobutyl ketone, methyl sec-butyl ketone, pinacolone,methyl pentyl ketone, methyl hexyl ketone, methyl heptyl ketone, methyloctyl ketone, methyl decyl ketone, methyl dodecyl ketone, methylpentadexyl ketone, diethyl ketone, ethyl hexyl ketone, di-n-butylketone, cyclopentanone, cyclohexanone, cycloheptanone, cyclopentenone,methyl vinyl ketone, methyl 2-methyl-1-propenyl ketone, ethyl 2-butynylketone, etc.; halogen-containing aliphatic ketones such as chloromethylethyl ketone, bromomethyl ethyl ketone, etc.; oxygen, sulfur ornitrogen-containing ketones such as methyl 2-hydroxyethyl ketone, methylmethoxymethyl ketone, methyl phenoxymethyl ketone, methylmethylthiomethyl ketone, methyl phenylthiomethyl ketone, methylN,N-dimethylaminomethyl ketone, etc.; optionally substituted benzenering-containing ketones such as acetophenone, methyl p-tolyl ketone,methyl 2,4-dimethylphenyl ketone, methyl m-methoxyphenyl ketone, methylm-phenoxyphenyl ketone, methyl 2,4-dichlorophenyl ketone, methylp-bromophenyl ketone, ethyl o-hydroxyphenyl ketone, methylp-(N,N-dimethylamino)phenyl ketone, etc.; arylalkyl, arylalkenyl orarylalkynyl-containing ketones such as methyl benzyl ketone, methyl2-phenylethyl ketone, benzalacetone, etc.; and thienyl orfuryl-containing ketones such as 2-acetylthiophene, 2-acetylfuran, etc.

Of the above Compounds (III), the aldehydes are referred to as aldehydeCompound (III-1) and the ketones as ketone Compound (III-2) hereinafter.

Examples of Compound (IV) include 2,3-dichloro-1-propene,2,3-dibromo-1-propene, 2,3diiodo-1-propene, 2-chloro-3-bromo-1-propene,2-chloro-3-iodo-1-propene, 2-bromo-3-chloro-1-propene,2-bromo-3-iodo-1-propene, 2-iodo-3-chloro-1-propene, and2-iodo-3-bromo-1-propene.

Commercially available zinc in a variety of forms may be used as thezinc for the present reaction, and zinc in a powder or granular from ispreferred. In particular, zinc in a powder form is more preferred.

The amount of the zinc to be used is 1 to 4 parts by mole, preferably1.2 to 2 parts by mole, based on the aldehyde Compound (III-1) and 1 to10 parts by mole, preferably 2 to 6 parts by mole, based on the ketoneCompound (III-2).

The amount of water to be used is 1 to 24 parts by weight, preferably 2to 9 parts by weight, based on Compound (III).

The amount of Compound (IV) to be used is usually 1 to 10 parts by molebased on the ketone Compound (III-2) and 1 to 4 parts by mole based onthe aldehyde Compound (III-1).

The reaction of dehalogenation in the step 1 may be carried out in anorganic solvent as required. Examples of such an organic solvent arediethyl ether, tetrahydrofuran, dioxane, toluene, benzene,monochlorobenzene, ethylene dichloride, chloroform, ethyl acetate,methanol, etc.

The amount of the organic solvent used is not specially limited.However, it is preferably not more than 5 parts by weight, morepreferably not more than 3 parts by weight based on the water.

The reaction temperature is in a range of 0° to 100° C., preferably 20°to 60° C.

The reaction time is usually 1 to 24 hours.

In addition, the reaction time can be shortened by adding a small amountof an acid, such as acetic acid, hydrochloric acid, hydrobromic acid,sulfuric acid, phosphoric acid, or the like.

Concerning the amount of the acid added in terms of a concentration inan aqueous solution thereof, when the aldehyde Compound (III-1) is used,the use of not more than 5% by weight of acetic acid or not more than0.1% by weight of hydrochloric acid, hydrobromic acid, sulfuric acid orphosphoric acid is preferred. When the ketone Compound (III-2) is used,the use of not more than 20% by weight of acetic acid or not more than1% by weight of hydrochloric acid, hydrobromic acid, sulfuric acid orphosphoric acid is preferred.

After the haloallylcarbinol Compound (II)-producing reaction iscompleted, the resultant mixture is treated in an ordinary manner, e.g.filtered, separated, concentrated or distilled, whereby thehaloallylcarbinol Compound (II) can be obtained.

For step 2 for the production of the propargylcarbinol Compound (I) bydehydrohalogenation of the haloallylcarbinol Compound (II), a suitablecombination of a base and a solvent is required.

Examples of the combination are:

(1) a polar aprotic solvent and an alkali metal hydroxide or alkalimetal alkoxide,

(2) a solvent selected from the group consisting of a mixed solvent of ahydrophobic hydrocarbon with water, a mixed solvent of a hydrophobichalogenated hydrocarbon with water, and water, and an alkali metalhydroxide in the presence of a phase transfer catalyst, and

(3) an organic solvent and an alkali metal hydroxide or alkali metalalkoxide in the presence of a diamine.

Examples of the alkali metal hydroxide used in the reaction at the step2 are sodium hydroxide, potassium hydroxide, etc. Examples of the alkalimetal alkoxide are sodium methoxide, sodium ethoxide, potassiumt-butoxide, etc.

Examples of the polar aprotic solvent used in the above combination (1)are acetonitrile, N,N-dimethylacetamide, N,N-dimethylformamide,N-methyl-2-pyrrolidone, dimethylsulfoxide, and hexamethylphosphoric acidtriamide, etc.

Examples of the hydrophobic hydrocarbon and the hydrophobic halogenatedhydrocarbon used in the above combination (2) are pentane, hexane,benzene, toluene, xylene, methylene chloride, chloroform, ethylenedichloride, and monochlorobenzene, etc.

Examples of the phase transfer catalyst are organic quaternary ammoniumsalts such as tetra-n-butylammonium bromide, tetra-n-butylammoniumchloride, tetra-n-pentylammonium bromide, tetra-n-pentylammonium iodideand benzyltriethylammonium chloride, and polyethylene glycols having amolecular weight of 200, 300, 600 or the like.

Examples of the organic solvent used in the above combination (3) areethyl ether, tetrahydrofuran, dioxane, diglyme, triglyme, triethylamine,pyridine and such solvents as are specified concerning the combinations(1) and (2).

Examples of the diamine are ethylenediamine,N,N,N',N'-tetramethylethylenediamine, 1,2-diaminopropane,1,3-diaminopropane, 1,4-diaminobutane, 1,6-diaminohexane,1,8-diazabicyclo[5,4,0]undec-7-ene, 1,5-diazabicyclo[4,3,0]non-5-ene,and 1,4-diazabicyclo-[2,2,2]octane. When ethylenediamine,1,2-diaminopropane or 1,3-diaminopropane is used, the solvent is notnecessarily required.

The amount of the base is usually 1 to 10 parts by mole, preferably 1 to4 parts by mole, based on the haloallylcarbinol Compound (II).

The amount of the solvent other than water is not specially limited.However, it is usually 0.1 to 20 parts by weight based on thehaloallylcarbinol Compound (II).

When water is used, its amount is usually 1 to 5 parts by weight basedon the alkali metal hydroxide.

The amount of the phase transfer catalyst in the combination (2) is 0.5to 10 parts by mole, preferably 0.5 to 5 parts by mole, based on thehaloallylcarbinol Compound (II).

The amount of the diamine in the combination (3) is usually 1 to 20parts by mole, preferably 1 to 15 parts by mole base don thehaloallylcarbinol Compound (II).

The reaction temperature of the above step 2 is usually in a range of-20° to 100° C., preferably 0° to 60° C.

The reaction time is not specially limited, and the reaction can bequenched when the haloallylcarbinol Compound (II), a starting material,is not detected any longer.

After the reaction, the resultant mixture is treated, i.e. by filtering,addition of water, extraction, separation, concentration ordistillation, whereby the propargylcarbinol Compound (I) can beobtained.

In the present invention, the formation of a by-product, an allenecompound of the formula (V) which is an isomer of the propargylcarbinolCompound (I), is low, and the propargylcarbinol Compound (I) can beobtained highly selectively. ##STR6##

The propargylcarbinol Compound (I) obtained according to theabove-detailed process is useful as a compound shown below or as anintermediate therefor. ##STR7##

The present invention is explained further in detail hereinbelow byreference to the Examples.

EXAMPLE 1

45.23 Grams of 2,3-dichloro-1-propene were added dropwise to a mixtureof 20.00 g of cyclohexanone, 60 g of toluene, 60 g of water and 26.65 gof zinc powder at 35° C., and after the addition, the resultant mixturewas maintained at the same temperature for 5 hours. After the reactionwas completed, zinc-derived insolubles were filtered off, and theresultant filtrate was separated. The organic phase thereof was washedwith a 7% sodium carbonate aqueous solution, and dried over magnesiumsulfate. The desiccant was filtered off, and the resultant toluenesolution was concentrated under reduced pressure to give 32.75 g of1-(2'-chloroallyl)-1-cyclohexanol; n_(D) ²⁰ =1.495, EI-MS m/e 156 (M-H₂O⁺), 158 (M-H₂ O+2⁺).

10.00 Grams of the 1-(2'-chloroallyl)-1-cyclohexanol obtained above weredissolved in 94 g of N,N-dimethylformamide, and 9.65 g of potassiumhydroxide in a flake form were added. The mixture was stirred at roomtemperature for 6 hours, and neutralized with a 20% acetic acid aqueoussolution. The resultant mixture was subjected to extraction withtoluene. The toluene phase was washed with water and dried overmagnesium sulfate. The desiccant was filtered off and the toluene wasdistilled off under reduced pressure to give 7.68 g of1-propargyl-1-cyclohexanol; m.p.=53°-54° C., FI-MS m/e 138(M⁺)(Propargyl compound/allene compound=100.0/0.0),

bp 48°-49° C./1 mmHg FI-MS m/e 138 (M⁺), 120 (M-H₂ O⁺) IR (neat) 3440,3320, 2120 cm⁻¹, ¹ H-NMR (CDCl₃, internal standard TMS), δ 1.25-1.70 (m,10H), 1.83 (2, 1H), 2.08 (t, 1H, J=2.6Hz), 2.36 (d, 2H, J=2.6Hz).

EXAMPLE 2

45.23 Grams of 2,3-dichloro-1-propene were added dropwise to a mixtureof 20.00 g of methyl 2-methyl-1-propenyl ketone, 60 g of toluene, 60 gof water and 26.65 g of zinc powder at 35° C., and after the addition,the resultant mixture was maintained at the same temperature for 5hours. After the reaction was completed, zinc-derived insolubles werefiltered off, and the filtrate was separated. The organic phase waswashed with 7% sodium carbonate aqueous solution and dried overmagnesium sulfate. The desiccant was filtered off and the toluene wasdistilled off under reduced pressure. The resultant oily substance waspurified by silica gel column chromatography to give 31.11 g of2-chloro-4,6-dimethyl-1,5-heptadien-4-ol; n_(D) ²⁵ =1.474, FI-MS m/e174(M), 176(M+2).

10.00 Grams of the 2-chloro-4,6-dimethyl-1,5-heptadien-4-ol obtainedabove were dissolved in 94 g of N,N-dimethylformamide, and 9.65 g ofpotassium hydroxide in a flake form were added. The resultant mixturewas stirred at room temperature for 4 hours and neutralized with a 20%acetic acid aqueous solution, and the resultant mixture was subjected toextraction with toluene. The toluene phase was washed with water andthen dried over magnesium sulfate. The desiccant was filtered off, andthen the toluene was distilled off under reduced pressure. The resultantoily substance was purified by silica gel column chromatography to give6.32 g of methyl 2-methylallylpropargylcarbinol; n_(D) ²⁵ =1.496, FI-MSm/e 138 (M⁺) (Propargyl compound/allene compound=100.0/0.0).

EXAMPLE 3

33.26 of 2,3-dichloro-1-propene were added dropwise to a mixture of20.00 g of acetophenone, 40 g of ethylene dichloride, 60 g of 5% aceticacid and 19.52 g of zinc powder at 50° C., and the resultant mixture wasallowed to react at the same temperature for 10 hours. After thereaction was completed, zinc-derived insolubles were filtered off, andthe resultant filtrate was separated. The organic phase was washed with7% sodium carbonate aqueous solution and dried over magnesium sulfate.The desiccant was filtered off, and the ethylene dichloride wasdistilled off under reduced pressure. The resultant oily substance waspurified by silica gel column chromatography to give 22.24 g of2-chloro-4-phenyl-1-penten-4-ol; n_(D) ²⁵ =1.536, FI-MS m/e 178(M-H₂O⁺), 180 (M-H₂ O+2⁺).

20.00 Grams of the 2-chloro-4-phenyl-1-penten-4-ol were dissolved in 50g of toluene, and 30.5 g of a 40% sodium hydroxide aqueous solution and65.57 g of tetra-n-butylammonium bromide were added. The mixture wasallowed to react at 50° C. for 30 hours and then was subjected toseparation. The organic phase was washed with water, and the toluene wasdistilled off under reduced pressure. The resultant oily substance waspurified by silica gel column chromatography to give 11.37 g of4-phenyl-1-pentyn-4-ol; n_(D) ²¹ =1.537 FI-MS m/e 160(M⁺) (Propargylcompound/allene compound 100.0/0.0).

EXAMPLE 4

47.53 Grams of 2,3-dibromo-1-propene were added dropwise to a mixture of15.00 g of 2-acetylthiophene, 30 g of toluene, 50 g of 0.01%hydrochloric acid and 15.55 g of zinc powder at 45° C., and the mixturewas allowed to react at the same temperature for 9 hours. After thereaction was completed, zinc-derived insolubles were filtered off, andthe resultant filtrate was subjected to separation. The organic phasewas washed with a 7% sodium carbonate aqueous solution, and the toluenewas distilled off under reduced pressure. The resultant oily substancewas purified by silica gel column chromatography to give 15.55 g ofα-(2-bromo-2-propenyl)-α-(2-thiophene)ethanol; n_(D) ²⁵ =1.539, FI-MSm/e 246(M), 248(M+2).

12.00 Grams of the α-(2-bromo-2-propenyl)-α-(2-thiophene)ethanolobtained above were dissolved in 108 g of N-methyl-2-pyrrolidone, and6.30 g of sodium methylate were added. The mixture was allowed to reactat 40° C. for 2 hours and then neutralized with concentratedhydrochloric acid, and insolubles were filtered off. An oily substanceobtained by concentrating the filtrate under reduced pressure waspurified by silica gel column chromatography to give 5.77 g ofα-propargyl-α-(2-thiophene)ethanol; n_(D) ²⁵ =1.516, FI-MS m/e 166(M)(Propargyl compound/allene compound 100.0/0.0).

EXAMPLE 5

5.00 Grams of 2-iodoallylmethyl-α-naphthylcarbinol were dissolved in 50g of dimethylformamide, and 1.18 g of sodium hydroxide in a flake formwere added. The resultant mixture was stirred at room temperature for 8hours. After the reaction was completed, the reaction mixture wasneutralized with concentrated hydrochloric acid, insolubles werefiltered off, and the remaining filtrate was concentrated under reducedpressure. The concentration residue was subjected to extraction withtoluene, and washed with a 7% sodium carbonate aqueous solution. Then,the toluene was distilled off under reduced pressure to give 2.77 g ofmethyl-α-naphthylpropargylcarbinol; n_(D) ²⁵ =1.5141, FI-MS m/e 210 (M)(Propargyl compound/allene compound 100.0/0.0).

EXAMPLE 6

58.30 Grams of 2,3-dichloro-1-propene were added dropwise to a mixtureof 30.00 g of heptanol, 90 g of toluene, 120 g of water and 34.35 g ofzinc powder at 45° C., and then the resultant mixture was allowed toreact at the same temperature for 10 hours. After the reaction finished,zinc-derived insolubles were filtered off, and the resultant filtratewas subjected to separation. The organic phase was washed with a 7%sodium carbonate aqueous solution and then dried over sodium sulfate.The desiccant was filtered off, and then the toluene was distilled offunder reduced pressure to give 47.14 g of 2-chloroallyl-n-hexylcarbinol.The results were as follows.

Yield 94.1% bp 74°-75° C./0.7 mmHg n_(D) ²⁰ 1.460 FI-MS m/e 190 (M⁺),192 (M+2⁺) IR (neat) 3370, 1640 cm⁻¹, ¹ H-NMR (CDCl₃, internal standardTMS), δ 0.89 (m, 3H), 1.30-1.74 (m, 10H), 1.82 (brs, 1H), 2.38-2.52 (m,2H), 3.93 (m, 1H), 5.25 (m, 1H), 5.28 (d, 1H, J=1.3Hz).

20.00 Grams of the 2-chloroallyl-n-hexylcarbinol obtained above weredissolved in 200 g of N,N-dimethylformamide, and 8.39 g of sodiumhydroxide in a flake form were added. The resultant mixture was stirredat 25° C. for 10 hours. After the reaction was completed, the reactionmixture was neutralized with concentrated hydrochloric acid, andinsolubles were filtered off. After the filtrate was concentrated underreduced pressure, the concentration residue was subjected to extractionwith toluene, washed with a 7% sodium carbonate aqueous solution andthen dried over sodium sulfate. The desiccant was filtered off, and thetoluene was distilled off. The resultant oily substance was distilledunder reduced pressure to give 15.70 g of n-hexylpropargylcarbinol. Theresults were as follows.

Yield 97.0% (propargyl compound/allene compound 98.0/2.0) bp 66.5°-68.5°C./0.8 mmHg n_(D) ²¹ 1.449 FI-MS m/e 154 (M⁺), 136 (M-H₂ O⁺) IR (neat)3380, 3310, 2120 cm⁻¹, ¹ H-NMR (CDCl₃, internal standard TMS), δ 0.89(m, 3H), 1.29-1.56 (m, 10H), 2.06 (t, 1H, J=2.6Hz), 2.20 (d, 1H,J=4.9Hz), 2.27-2.47 (m, 2H), 3.75 (m, 1H).

EXAMPLE 7

125.40 Grams of 2,3-dichloro-1-propene were added dropwise to a mixtureof 60.00 g of benzaldehyde, 180 g of toluene, 240 g of 5% acetic acidand 73.88 g of zinc powder at 45° C., and then the mixture was allowedto react at the same temperature of 3 hours. After the reaction wascompleted, zinc-derived insolubles were filtered off, and the resultantfiltrate was subjected to separation. The organic phase was washed witha 7% sodium carbonate aqueous solution and dried over sodium sulfate.The desiccant was filtered off, and then the toluene was distilled offunder reduced pressure to give 98.23 g of 2-chloroallylphenylcarbinol.The results were as follows.

Yield 95.2% bp 103°-104° C./2.5 mmHg n_(D) ¹⁹ 1.543 FI-MS m/e 182 (M⁺),184 (M+2⁺) IR (neat) 3390, 1640 cm⁻¹, ¹ H-NMR (CDCl₃, internal standardTMS), δ 2.22 (brs, 1H), 2.60-2.80 (m, 2H), 5.00 (dd, 1H, J=8.9, 4.3Hz),5.20 (d, 1H, J=1.0Hz), 5.26 (d, 1H, J=1.3Hz), 7.23-7.38 (m, 5H).

40.00 Grams of the 2-chloroallylphenylcarbinol obtained above weredissolved in 400 g of N,N-dimethylformamide, and 17.52 g of sodiumhydroxide in a flake form were added. The mixture was stirred at 25° C.for 7 hours. After the reaction was completed, the reaction mixture wasneutralized with concentrated hydrochloric acid, and insolubles werefiltered off. The filtrate was concentrated under reduced pressure, andthen the concentration residue was subjected to extraction with toluene,washed with a 7% sodium carbonate aqueous solution and dried over sodiumsulfate. The desiccant was filtered off, and the toluene was distilledoff under reduced pressure. The resultant oily substance was distilledunder reduced pressure to give 30.84 g of phenylpropargylcarbinol. Theresults were as follows.

Yield 96.3% (propargyl compound/allene compound 93.2/6.8) bp 74°-76°C./0.5 mmHg n_(D) ²⁰ 1.546 FI-MS m/e 146 (M⁺), 128 (M-H₂ O⁺) IR (neat)3390, 3300, 2120 cm⁻¹, ¹ H-NMR (CDCl₃, internal standard TMS), δ 2.06(t, 1H, J=2.6Hz), 2.47 (d, 1H, J=3.6Hz), 2.63 (dd, 2H, J=6.3, 2.6Hz),4.85 (m, 1H), 7.24-7.40 (m, 5H).

EXAMPLE 8

47.50 Grams of 2,3-dichloro-1-propene were added dropwise to a mixtureof 20.00 g of crotonaldehyde, 40 g of ethylene dichloride, 60 g of 3%acetic acid and 18.65 g of zinc powder at 40° C., and the resultantmixture was allowed to react at the same temperature for 5 hours. Afterthe reaction was completed, zinc-derived insolubles were filtered offand, the resultant filtrate was subjected to separation. The organicphase was washed with a 7% sodium carbonate aqueous solution and driedover magnesium sulfate. The desiccant was filtered off, and the ethylenedichloride was distilled off under reduced pressure to give 37.15 g of2-chloro-1,5-heptadien-4-ol; n_(D) ²⁵ =1.471, FI-MS m/e 146(M⁺),148(M+2⁺).

20.00 Grams of the 2-chloro-1,5-heptadien-4-ol obtained above weredissolved in 50 g of toluene, and 40.9 g of a 40% sodium hydroxideaqueous solution and 87.94 g of tetra-n-butylammonium bromide wereadded. The resultant mixture was allowed to react at 50° C. for 24 hoursand then separated, and the organic phase was washed with water. Thetoluene was distilled off under reduced pressure. The resultant oilysubstance was purified by silica gel column chromatography to give 10.72g of hept-5-en-1-yn-4-ol; n_(D) ²⁵ =1.493, FI-MS m/e 110(M⁺), propargylcompound/allene compound 94.0/6.0.

EXAMPLE 9

49.93 Grams of 2,3-dibromo-1-propene were added dropwise to a mixture of20.00 g of phenylacetaldehyde, 40 g of toluene, 60 g of 0.01%hydrochloric acid and 16.33 g of zinc powder at 30° C., and the mixturewas allowed to react at the same temperature for 3 hours. After thereaction was completed, zinc-derived insolubles were filtered off, andthe resultant filtrate was separated. The organic phase was washed witha 7% sodium carbonate aqueous solution, and the toluene was distilledoff under reduced pressure. The resultant oily substance was purified bysilica gel column chromatography to give 24.01 g of2-bromo-5-phenyl-1-penten-4-ol; n_(D) ²⁵ =1.536, FI-MS m/e 240(M⁺),242(M+2⁺).

20.00 Grams of the 2-bromo-5-phenyl-1-penten-4-ol obtained above weredissolved in 160 g of N-methyl-2-pyrrolidone, and 11.20 g of sodiummethylate were added. The mixture was allowed to react at 30° C. for 14hours and then was neutralized with concentrated hydrochloric acid.Insolubles were filtered off, and the filtrate was concentrated underreduced pressure. The resultant oily substance was purified by silicagel column chromatography to give 9.96 g of 5-phenyl-1-pentyn-4-ol,n_(D) ²⁵ =1.519, FI-MS m/e 160(M⁺), propargyl compound/allene compound97.9/2.1.

EXAMPLE 10

19.5 Grams of 2-chloroallylphenylcarbinol were dissolved in 100.0 g of1,3-diaminopropane, and 9.2 g of sodium methylate were added. Themixture was allowed to react at 30° C. for 16 hours. Then, the reactionmixture was neutralized with concentrated hydrochloric acid, andinsolubles were filtered off. The filtrate was concentrated underreduced pressure, and the resultant oily substance was purified bysilica gel column chromatography to give 12.6 g ofphenylpropargylcarbinol, n_(D) ²⁰ =1.546, FI-MS m/e 146(M⁺), propargylcompound/allene compound=93.0/7.0.

EXAMPLE 11

5.00 Grams of 2-iodoallyl-α-naphthylcarbinol were dissolved in 50 g ofdimethylformamide, and 1.23 g of sodium hydroxide in a flake form wereadded. The mixture was stirred at room temperature for 6 hours. Afterthe reaction was completed, the reaction mixture was neutralized withconcentrated hydrochloric acid, insolubles were filtered off, and thefiltrate was concentrated under reduced pressure. The concentrationresidue was subjected to extraction with toluene and washed with a 7%sodium carbonate aqueous solution, and then the toluene was distilledoff under reduced pressure to give 2.78 g ofα-naphthylpropargylcarbinol; n_(D) ²⁵ =1.549, FI-MS m/e 196(M⁺).

EXAMPLES 12-34

Propargylcarbinol compounds (I) were produced from haloallylcarbinolcompounds (II) shown in Table 1 according to conditions described inExample 11. The results are shown in Table 1.

    TABLE 1      Haloallylcarbinol Base Solvent Reaction Reaction Propargylcarbinol (I)     Ex-  Amount  Amount  Amount tempera- time  Yield Propargyl compound/     ample Name (g) Name (g) Name (g) ture (°C.) (hr) Name (%) allene     compound n.sub.D MS       12 2-Chloroallyl- 30.00 NaOH 12.11 Ethylene- 121.28 25 8.5 Isopropylpro     paragyl- 94.9 97.7/2.3 1.447 FI-MS  isopropylcarbinol    diamine     carbinol   (20° C.) 112 (M.sup.+) 13 n-Butyl-2-chloro- 15.00 "     7.36 Dimethyl- 150 40 4 n-Butylpropargyl- 95.9  87.5/12.5 1.447 FI-MS     allylcarbinol    formamide    carbinol   (24° C.) 126 (M.sup.+)     14 2-Chloroallyl-n- " " 6.80 Dimethyl- " " " n-Pentylpropargyl- 96.6     87.6/12.4 1.449 FI-MS  pentylcarbinol    formamide    carbinol     (24° C.) 140 (M.sup.+) 15 2-Chloroallyl-n- 10.00 KOH 8.81     Dimethyl- 100 25 6 n-Hexylpropargyl- 94.9 90.6/9.4  hexylcarbinol     formamide    carbinol 16 2-Chloroallyl- 20.00 NaOH 8.48 Dimethyl- 200 "     10 Cyclohexylpropargyl- 99.0 99.5/0.5 1.486 FI-MS  cyclohexylcarbinol     formamide    carbinol   (20° C.) 152 (M.sup.+) 17 10-Chloro-2,6-     " " 6.99 Dimethyl- " " " 2,6-Dimethylundeca- " Unknown 1.488 FI-MS     dimethyl-2,6,10-    formamide    2,6-dien-10-yn-8-ol   (21° C.)     192 (M.sup.+)  undecatrien-8-ol 18 5-Chloro-2-phenyl-5- " " 7.59     Dimethyl- " 20 8 2-Phenyl-5-hexyn-3- 93.3 100.0/0.0       mp FD-MS  hexen-3-ol    formamide    ol   64° C. 174 (M.sup.+)     19 trans-5-Chloro-1- 24.43 " 9.37 Dimethyl- 244.3 25 " trans-1-Phenyl-hex     a- 92.9 98.2/1.8 1.573 FD-MS  phenyl-1,5-hexadien-    formamide     1-en-5-yn-3-ol   (21°      C.) 172 (M.sup.+)  3-ol 20 2-Chloroallylphenyl- 40.00 NaOH 17.52     Dimethyl- 400 25 7 Phenylpropargyl- 96.3 93.2/6.8  carbinol    formamide        carbinol 21 2-Chloroallyl-p- 15.00 " 6.12 Dimethyl- 150 40 4 Propargyl     -p- 93.9      83.9/16.1 1.543 FD-MS  tolylcarbinol    formamide    tolylcarbinol     (24° C.) 160 (M.sup.+) 22 2-Chloroallyl-p- " " 5.64 Dimethyl- " "     " p-Methoxyphenyl- 98.3  84.2/15.8 1.553 FD-MS  methoxyphenylcarbinol     formamide    propargylcarbinol   (24° C.) 176 (M.sup.+) 23     2'-Chloroallyl-3,4- 23.00 " 8.12 Dimethyl- 230 25 10 3,4-Methylenedioxy-     97.0 91.6/8.4 1.565 FD-MS  methylenedioxyphenyl-    formamide     phenylpropargyl-   (21° C.) 190 (M.sup.+)  carbinol     carbinol 24 2'-Chloroallyl-3,4- " " " Dimethyl- " 40 4 3,4-Methylenedioxy     - 96.5      85.2/14.8  methylenedioxyphenyl-    formamide    phenylpropargyl-     carbinol        carbinol 25 2-Chloroallyl-p- " " 8.47 Dimethyl- " 25 10     p-Chlorophenyl- 99.5 92.1/7.9 1.557 FI-MS  chlorophenylcarbinol     formamide    propargylcarbinol   (21° C.) 180 (M.sup.+)        182 (M +      2.sup.+) 26 2-Chloroallyl-p- " " " Dimethyl- " 40 3 p-Chlorophenyl-     95.1  86.1/13.9  chlorophenylcarbinol    formamide    propargylcarbinol      27 2'-Chloroallyl-2,4- 15.00 " 4.76 Dimethyl- 150 25 12 2,4-Dichlorophen     yl- 92.9 90.6/9.4 mp FD-MS  dichlorophenyl-    formamide    propargylcarb     inol   44.5-45.5° C. 214 (M.sup.+)  carbinol            216 (M +     2.sup.+)              218 (M + 4.sup.+) 28 2'-Chloroallyl-2- 20.00 "     8.48 Dimethyl- 200 " " Propargyl-2- 90.4 91.0/9.0 1.559 FI-MS  thienylcar     binol    formamide    thienylcarbinol   (20° C.) 152 (M.sup.+) 29     1-(2'-Chloroallyl)- 20.00 NaOH 8.57 Dimethyl- 200 25 10 1-Propargylcyclo-      92.9 100.0/0.0        cyclohexan-1-ol    formamide    hexan-1-ol 30 2-Chloro-4-methyl-1- "     " 9.06 Dimethyl- " " 12 4-Methyl-1-octyn-4- 91.4 " 1.446 FI-MS  octen-4-o     l    formamide    ol   (21°      C.) 140 (M.sup.+) 31 5-Chloro-3-methyl-1- " " 7.12 Dimethyl- " " "     3-Methyl-1-phenyl-5- 98.8 " 1.525 FD-MS  phenyl-5-hexen-3-ol    formamide         hexyn-3-ol   (20° C.) 188 (M.sup.+) 32 5-Chloro-3-methyl-1-     18.49 " 6.64 Dimethyl- 184.9 " " 3-Methyl-1-phenyl- 97.7 " 1.567 FD-MS     phenyl-1,5-hexadien-    formamide    hexan-1-en-5-yn-3-ol   (21°     C.) 186 (M.sup.+)  3-ol 33 4-Chloro-2-phenyl-4- 20.00 " 8.14 Dimethyl-     200 " 5 2-Phenyl-4-pentyn-2- 96.0 " 1.537 FI-MS  penten-2-ol    formamide         ol   (21° C.) 160 (M.sup.+) 34 5-(2'-Chloroallyl)- 17.50 "     6.40 Dimethyl- 175 " 12 5-Propargylnonan-5- 96.6 " 1.452 FI-MS  nonan-5-o     l    formamide    ol   (21°      C.) 182 (M.sup.+)

EXAMPLE 35

58.30 Grams of 2,3-dichloro-1-propene were added dropwise to a mixtureof 30.00 g of heptanal, 90 g of toluene, 120 g of 5% acetic acid and34.35 g of zinc powder at 45° C., and then the mixture was allowed toreact at the same temperature for 3 hours. After the reaction wascompleted, zinc-derived insolubles were filtered off, and the resultantfiltrate was subjected to separation. The organic phase was washed witha 7% sodium carbonate aqueous solution and dried over sodium sulfate.The desiccant was filtered off, and then the toluene was distilled offunder reduced pressure to give 46.31 g of 2-chloroallyl-n-hexylcarbinol.The yield thereof was 92.4%.

EXAMPLE 36

40.00 Grams of 2-chloroallylphenylcarbinol were dissolved in 400 g ofdimethylformamide, and 36.85 g of potassium hydroxide in a flake formwere added. The mixture was stirred at room temperature for 2 hours andthen neutralized with a 20% acetic acid aqueous solution. The resultantmixture was subjected to extraction with toluene. The toluene phase waswashed with water and then dried over magnesium sulfate. The desiccantwas filtered off, and the toluene was distilled off under reducedpressure to give 31.35 g of phenylpropargylcarbinol, n_(D) ²⁰ =1.546,FI-MS m/e 146 (M⁺), propargyl compound/allene compound=92.3/7.7.

EXAMPLES 37-52

Haloallylcarbinol compounds (II) were produced from aldehyde compounds(III-1) shown in Table 2 according to conditions described in Example 7.The results are shown in Table 2.

    TABLE 2        Reaction Re-  Aldehyde (III-1)  tempera- action Haloallylcarbinol     (II) Ex-  Amount Organic ture time  Yield mp bp     ample Name (g)     solvent (°C.) (hr) Name (%) (°C.) (°C.) n.sub.D MS     IR .sup.1      H-NMR (CDC13, internal standard TMS)                             37     Acetaldehyde 30.00 Ethyl 32 3 2-Chloro- 97.6  42 1.459 FI-MS neat     δ 1.25(d, 3H, J=7.1Hz), 1.91(brs, 1H), 2.39-2.54    ether     allylmethyl-   (5 mm (25° C.) 120 (M.sup.+) 3370 cm.sup.-1 (m,     2H), 4.15(m, 1H), 5.24(m, 1H), 5.27(d, 1H,       carbinol   Hg)  122 (M     + 2.sup.+) 1640 cm.sup.-1 J=1.3Hz) 38 Propion- " Ethyl " " 2-Chloro-     98.0  54 1.457 FI-MS neat δ 0.98(t, 3H, J=7.1Hz), 1.45-1.61(m,     2H), 1.82  aldehyde  ether   allylethyl-   (5 mm (25° C.) 134     (M.sup.+) 3380 cm.sup.-1 (brs, 1H), 2.39-2.53(m, 2H), 3.82-3.91(m, 1H),          carbinol   Hg)  136 (M + 2.sup.+) 1640 cm.sup.-1 5.25(m, 1H),     5.27(d, 1H, J=1.3Hz) 39 2-Methyl- " Ethyl " " 2-Chloro- 99.7  38-40     1.459 FI-MS neat δ 0.96(d, 6H, J=6.9Hz), 1.68-1.80(m, 2H), 2.36-     propion-  ether   allylisopro-   (5 mm (20° C.) 148 (M.sup.+)     3420 cm.sup.-1 2.53(m, 2H), 3.72(ddd, 1H, J=8.9, 5.3, 3.6Hz),  aldehyde        pylcarbinol   Hg)  150 (M + 2.sup.+) 1640 cm.sup.-1 5.26(dt, 1H,     J=1.3, 0.7Hz), 5.29(d, 1H, J=1.3Hz) 40 Pentanal " Toluene 35 1.5     Butyl-2- 98.9  55-57 1.459 FD-MS neat δ 0.93(t, 3H, J=7.0Hz),     1.29-1.54(m, 6H), 1.74       chloroallyl-   (3 mm (25° C.) 163 (M     + H.sup.+) 3380 cm.sup.-1 (brs, 1H), 2.34-2.52(m, 2H), 3.93(m, 1H),     5.25(m,       carbinol   Hg)  165 (M + H + 2.sup.+) 1640 cm.sup.-1 1H),     5.27(d, 1H, J=1.3Hz) 41 Hexanal " " " 2 2-Chloro- 99.0  66 1.459 FD-MS     neat δ 0.89(m, 3H), 1.25-1.50(m, 8H), 1.76(brs, 1H),     allylpentyl-   (3 mm (25° C.) 177 (M + H.sup.+) 3380 cm.sup.-1     2.36-2.55(m, 2H), 3.92(m, 1H), 5.24(m, 1H), 5.29       carbinol   Hg)     179 (M + H + 2.sup.+) 1640 cm.sup.-1 (d, 1H, J=1.3Hz) 42 Cyclohexane- "     " 45 3 2-Chloro- 95.7  72-75 1.490 FI-MS 188 neat δ 0.99-1.45(m,     6H), 1.67-1.85(m, 6H), 2.37-2.55  carbaldehyde     allylcyclo-   (0.5 mm     (19° C.) (M.sup.+), 190 3400 cm.sup.-1 (m, 2H), 3.71(dt, 1H,     J=3.6, 9.1Hz), 5.25(m, 1H),       hexylcarbinol   Hg)  (M + 2.sup.+ )     1635 cm.sup.-1 5.29(d, 1H, J=1.3Hz)            170 (M - H.sub.2 O.sup.+)                172 (M - H.sub.2 O +            2.sup.+) 43 Citral 30.00     Toluene 45 3 2-Chloro- 95.7  117-119 1.4919 FD-MS neat δ      1.60-1.75(m, 10H), 1.98-2.20(m, 4H), 2.38-2.47       allyl   (0.8 mm     (21° C.) 228 (M.sup.+) 3370 cm.sup.-1 (m, 1H), 2.52-2.63(m, 1H),     4.72(m, 1H), 5.05-5.21       2',6'-di-   Hg)  230 (M + 2.sup.+) 1640     cm.sup.-1 (m, 2H), 5.23(m, 1H), 5.26(d, 1H, J=1.0Hz)       methyl-1',5'-           heptadienyl-       carbinol 44 2-Phenyl- " " " " 2-Chloro- 94.9     48-56   FD-MS KBr δ      1.36(d, 3H, J= 6.9Hz), 1.84(brs, 1H), 2.28-2.40  propional-     allyl-1'-     210 (M.sup.+) method (m, 2H), 2.80(quint, 1H, J=6.9Hz),     4.03(ddd, 1H,  dehyde     phenylethyl-     212 3420 cm.sup.-1 J=7.6,     6.6, 5.0Hz), 5.20(d, 1H, J=0.7Hz),       carbinol     (M + 2.sup.+) 1640     cm.sup.-1 5.25(d, 1H, J=1.3Hz), 7.19-7.35(m, 5H) 45 Cinnamic " " " "     2-Chloro- 74.2  132-134 1.5761 FD-MS neat δ 2.10(brs, 1H),     2.55-2.70(m, 2H), 4.63(m, 1H),  aldehyde     allylstyryl-   (0.8 mm     (19° C.) 208 (M.sup.+) 3400 cm.sup.-1 5.27(m, 1H), 5.30(d, 1H,     J=1.3Hz), 6.21(dd, 1H,       carbinol   Hg)  210 (M + 2.sup.+) 1640     cm.sup.-1 J=15.8, 6.6Hz), 6.65(dd, 1H, J=15.8, 1.0Hz),     7.18-7.57(m, 5H) 46 p-Tolalde- " " 35 " 2-Chloro- 98.2  96-98 1.5338     FD-MS neat δ 2.21(brs, 1H), 2.33(s, 3H), 2.56-2.77(m, 2H),  hyde       allyl-p-   (0.5 mm (25° C.) 196 (M.sup.+) 3400 cm.sup.-1     4.95(dd, 1H, J=9.0, 4.9Hz), 5.19(m, 1H), 5.24(d,       tolylcarbinol     Hg)  198 (M + 2.sup.+) 1640 cm.sup.-1 1H, J=1.3Hz), 7.11-7.23(m, 4H) 47     p-Methoxy- " " " " 2-Chloro- 96.0  122-123 1.5455 FD-MS neat δ     1.97(brs, 1H), 2.59-2.81(m, 2H), 3.80(s, 3H),  benzaldehyde     allyl-p-       (0.6 mm (25° C.) 212 (M.sup.+) 3430 cm.sup.-1 4.98 dd, 1H,     J=8.7, 5.2Hz), 5.20(m, 1H), 5.26(d,       methoxy-   Hg)  214 (M +     2.sup.+) 1640 cm.sup.-1 1H, J=1.3Hz), 6.88(m, 2H), 7.28(m, 2H)     phenyl       carbinol 48 Piperonal " " 45 " 2-Chloro- 93.7 56-57   FD-MS     KBr δ 2.11(d, 1H, J= 2.6Hz), 2.57-2.79(m, 2H),       allyl-     226 (M.sup.+) method 4.94(m, 1H), 5.22(m, 1H), 5.27(d, 1H, J=1.3Hz),       3',4'-methyl-     228 3380 cm.sup.-1 5.95(s, 2H), 6.75-6.89(m, 3H)       enedioxy-     (M + 2.sup.+) 1640 cm.sup.-1       phenyl-     carbinol 49 p-Chloro- 30.00 Toluene 45 3 2-Chloro- 95.0 48-50   FD-MS     KBr δ 2.28(d, 1H, J=3.3Hz), 2.57-2.77(m, 2H),  benzaldehyde     allyl-     216 (M.sup.+) method 4.99(m, 1H), 5.20(m, 1H), 5.27(d, 1H,     J=1.3Hz),       p-chloro-     218 (M + 2.sup.+) 3390 cm.sup.-1 7.31(s,     4H)       phenyl-     220 (M + 4.sup.+) 1635 cm.sup.-1       carbinol 50     2,4- " " 35 " 2-Chloro- 93.6 41   FD-MS KBr δ 2.34(s, 1H),     2.44-2.56(m, 2H), 5.29(m, 1H),  Dichloro-     allyl-     250 (M.sup.+)     method 5.33(d, 1H, J=1.3Hz), 5.43(m, 1H), 7.08-7.27  benzaldehyde     2', 4'-di-     252 (M +      2.sup.+) 3420 cm.sup.-1 (m, 3H)       chlorophenyl-     254 (M +     4.sup.+) 1635 cm.sup.-1       carbinol 51 m-Phenoxy- " " 45 " 2-Chloro-     96.4  169-170 1.5804 FD-MS neat δ 2.17(brs, 1H), 2.60-2.78(m, 2H),     4.99(dd, 1H,  benzaldehyde     allyl-   (0.6 mm (25°      C.) 274(M.sup.+) 3410 cm.sup.-1 J=8.6, 4.6Hz), 5.21(m, 1H), 5.28(d, 1H,     J=       m-phenoxy-   Hg)  276 (M + 2.sup.+) 1635 cm.sup.-1 1.0Hz),     6.89-7.37(m, 9H)       phenyl-       carbinol 52 2-Thiophene- "  " " "     2-Chloro- 92.1  84-86 1.5585 FI-MS neat δ 2.39(d, 1H, J=3.3Hz),     2.73-2.92(m, 2H), 5.25-  carbaldehyde     allyl-2'-   (0.9 (19°     C.) 170 (M - H.sub.2 O.sup.+) 3390 cm.sup.-1 5.31(m, 3H), 6.98(m, 2H),     7.25(dd, 1H, J=5.0,        thienyl-   mmHg)  172 (M - 1640 cm.sup.-1     1.3Hz)       carbinol     H.sub.2 O +      2.sup.+)

EXAMPLE 53

56.53 Grams of 2,3-dichloro-1-propene were added dropwise to a mixtureof 25.00 g of cyclohexanone, 75 g of toluene, 100 g of 5% acetic acidand 34.35 g of zinc powder at 45° C., and then the mixture was allowedto react at the same temperature for 3 hours. After the reaction wascompleted, zinc-derived insolubles were filtered off, and the resultantfiltrate was subjected to separation. The organic phase was washed witha 7% sodium carbonate aqueous solution and dried over sodium sulfate.The desiccant was filtered off, and then the toluene was distilled offunder reduced pressure to give 44.05 g of1-(2'-chloroallyl)-1-cyclohexanol. The results were as follows.

Yield 99.0% bp 62°-65° C./0.5 mmHg n_(D) ²⁰ 1.4950 FI-MS m/e 156 (M-H₂O⁺), 158 (M-H₂ O+2⁺) IR (neat) 3460, 1630 cm⁻¹, ¹ H-NMR (CDCl₃, internalstandard TMS), δ 1.26-1.71 (m, 10H), 1.82 (s, 1H), 2.54 (s, 2H), 5.21(d, 1H, J=0.8Hz), 5.34 (d, 1H, J=0.8Hz).

EXAMPLES 54-65

Haloallylcarbinol compounds (II) were produced from ketone compounds(III-2) shown in Table 3 according to the conditions described inExample 53. The results are shown in Table 3.

                                      TABLE 3                                     __________________________________________________________________________                             Acetic acid                                                                            Amount of  Re-  Re-                                                  Con-     2,3-di-                                                                             Amount                                                                             action                                                                             actio                       Ketone (III-2) Organic solvent                                                                         centra-  chloro-1-                                                                           of   tempera-                                                                           n                           Ex-       Amount    Amount                                                                             tion                                                                              Amount                                                                             propene                                                                             zinc ture time                        ample                                                                             Name  (g)  Name (g)  (%) (g)  (g)   (g)  (°C.)                                                                       (hr)                        __________________________________________________________________________    54  Methyl n-                                                                           10.00                                                                              Toluene                                                                            30   5   40   22.15 13.05                                                                              45   5.5                             butyl                                                                         ketone                                                                    55   "    "    None  0   "   "    "     "    "    3                           56   "    "     "   "    10  "    33.23 19.58                                                                              "    "                           57  Methyl 2-                                                                           20.00                                                                              Toluene                                                                            60   5    80  29.96 17.65                                                                              45   5                               phenyl-                                                                       ethyl                                                                         ketone                                                                    58  Methyl 2-                                                                           20.00                                                                              Toluene                                                                            60   5    80  59.92 35.30                                                                              45   2                               phenyl-                                                                       ethyl                                                                         ketone                                                                    59   "    "     "   "    "   "    89.88 52.95                                                                              "    "                           60  Benzal-                                                                             30.00                                                                               "   90   "   120  45.54 26.83                                                                              "    "                               acetone                                                                   61   "    "     "   "    "   "    136.62                                                                              80.49                                                                              "    "                           62  Aceto-                                                                              30.00                                                                              Toluene                                                                            90    5  120  55.42 32.65                                                                              45   2                               phenone                                                                   63   "    "     "   "    "   "    110.84                                                                              65.30                                                                              "    "                           64   "    "     "   "    "   "    166.26                                                                              97.95                                                                              "    "                           65  di-n-Butyl                                                                          "    None  0   10  "    210.65                                                                              124.11                                                                             "    "                               ketone                                                                    __________________________________________________________________________    tertiary Haloallylcarbinol (II)                                                                                         .sup.1 H-NMR                              Yield mp bp                         (CDCl.sub.3, internal               Name  (%)   (°C.)                                                                     (°C.)                                                                       n.sub.D                                                                            Ms         IR    standard TMS)                       __________________________________________________________________________    2-Chloro-                                                                           52.2     54-56                                                                              1.461                                                                              FI-MS      neat  δ 0.92 (m, 3H), 1.25 (s,      4-methyl-      (5 mm                                                                              (20°C.)                                                                     177(M + H.sup.+)                                                                         3450 cm.sup.-1                                                                      3H), 1.32-1.57 (m, 6H),             1-octen-4-     Hg)       179(M + H + 2.sup.+)                                                                     1630 cm.sup.-1                                                                      1.86 (brs, 1H), 2.54 (m,            ol                       158(M - H.sub.2 O.sup.+)                                                                       2H), 5.22 (d, 1H,                                            160(M - H.sub.2 O + 2.sup.+)                                                                   J = 1.0Hz), 5.35 (d, 1H,                                                      J = 1.0Hz)                           "    77.3                                                                     "    94.0                                                                    5-Chloro-                                                                           29.9     126- 1.530                                                                              FI-MS      neat  δ 1.33 (s, 3H),                                                         1.82-1.88                           3-methyl-      128  (21° C.)                                                                    206(M - H.sub.2 O.sup.+)                                                                 3470 cm.sup.-1                                                                      (m, 3H), 2.61 (d, 2H,               1-phenyl-      (0.9      208(M - H.sub.2 O + 2.sup.+)                                                             1640 cm.sup.-1                                                                      J = 4.0Hz), 2.70-2.79 (m,           5-hexen-3-     mmHg)                      2H), 5.24 (m, 1H), 5.37             ol                                        (d, 1H, J = 1.3Hz), 7.15-                                                     7.32 (m, 5H)                        5-Chloro-                                                                           59.5                                                                    3-methyl-                                                                     1-phenyl-                                                                     5-hexen                                                                       3-ol                                                                           "    93.1                                                                    5-Chloro-3-                                                                         27.1          1.5648                                                                             FD-MS      neat  δ 1.46 (s, 3H), 1.68 (s,      methyl-1-           (19° C.)                                                                    222(M.sup.+)                                                                             3440 cm.sup.-1                                                                      1H), 2.70 (s, 2H), 5.25             phenyl-1,5-              224(M + 2.sup.+)                                                                         1630 cm.sup.-1                                                                      (d, 1H, J = 1.0Hz);                 hexadien-3-                               5.35 (d, 1H J =                     ol                                        1.0Hz), 6.33 (d, 1H,                                                          J = 15.8Hz), 6.65                                                             (d, 1H, J = 15.8Hz),                                                          7.09-7.43 (m,5H)                     "    78.8                                                                    4-Chloro-                                                                           42.4     84-85                                                                              1.5395                                                                             FI-MS      neat  δ 1.64 (s, 3H), 2.37                                                    (brs,                               2-phenyl       (0.5 (20° C.)                                                                    178(M - H.sub.2 O.sup.+)                                                                 3460 cm.sup.-1                                                                      1H), 2.82 (d, 1H,                   4-phenten-     mm Hg)    180(M - H.sub.2 O + 2.sup.+)                                                             1635 cm.sup.-1                                                                      J = 14.7Hz), 2.91 (d, 1H,           2-ol                                      J = 14.7Hz), 5.07 (d,1H,                                                      1.3Hz), 5.27 (d, 1H, J =                                                      1.3Hz), 7.22-7.47 (m, 5H)            "    71.5                                                                     "    93.7                                                                    5-(2'-                                                                              59.2     77-79                                                                              1.4613                                                                             FI-MS      neat  δ 0.91 (m, 6H), 1.32 (m,      chloro-        (0.5 (19° C.)                                                                    200(M - H.sub.2 O.sup.+)                                                                 3480 cm.sup.-1                                                                      8H), 1.51 (m, 4H), 1.78             allyl)-        mm Hg)    202(M- H.sub.2 O + 2.sup.+)                                                              1630 cm.sup.-1                                                                      (s, 1H), 2.53 (s, 2H),              nonan-5-ol                                5.21 (d, 1H, J = 1.0Hz),                                                      5.34 (d, 1H, J                      __________________________________________________________________________                                              = 1.0Hz)                        

What is claimed is:
 1. A process for producing a haloallylcarbinolcompound of the formula (II): ##STR8## where R¹ and R² independentlyrepresent a hydrogen atom; a C₁ -C₁₅ alkyl group which may besubstituted with at least one member selected from the group consistingof halogen atoms, a hydroxyl group, a phenyl group, a phenoxy group, aphenyl or phenoxy group substituted with at least one member selectedfrom the group consisting of halogen atoms and hydroxyl, alkoxy,phenoxy, dialkylamino and methylenedioxy groups, an aralkyloxy group, adialkylamino group, an alkylthio group, a phenylthio group, a biphenylgroup and a phenylalkyl group; a C₂ -C₁₅ alkenyl group which may besubstituted with at least one member selected from the group consistingof halogen atoms, a hydroxyl group, a phenyl group, a phenoxy group, aphenyl or phenoxy group substituted with at least one member selectedfrom the group consisting of halogen atoms and hydroxyl, alkoxy,phenoxy, dialkylamino and methylenedioxy groups, a dialkylamino group,an alkylthio group, a phenylthio group, a biphenyl group and aphenylalkyl group; a C₂ -C₁₅ alkynyl group which may be substituted withat least one member selected from the group consisting of halogen atoms,a hydroxyl group, a phenyl group, a phenoxy group, a phenyl or phenoxygroup substituted with at least one member selected from the groupconsisting of halogen atoms and hydroxyl, alkoxy, phenoxy, dialkylaminoand methylenedioxy groups, a dialkylamino group, an alkylthio group, aphenylthio group, a biphenyl group and a phenylalkyl group; a C₃ -C₁₅cycloalkyl group; a C₄ -C₁₅ cycloalkyl group; or a phenyl, naphthyl,furyl or thienyl group which may be substituted with at least one memberselected from the group consisting of halogen atoms and hydroxyl, alkyl,alkoxy, phenoxy, dialkylamino and methylenedioxy groups; or R¹ and R²together represent a C₂ -C₁₅ alkylene or alkenylene chain; with provisothat carbon atoms in the 1-positions of R¹ and R² are not togethertertiary carbon atoms and that when one of R¹ and R² is the furyl group,the other does not represent a hydrogen atom: which comprises reacting acarbonyl compound of the formula (III): ##STR9## where R¹ and R² are asdefined above, with a dihalopropene compound of the formula (IV):##STR10## where X¹ and X² independently represent a chlorine, in thepresence of zinc, water and an acid.
 2. A process according to claim 1,wherein said acid is at least one selected from the group consisting ofacetic acid, hydrochloric acid, hydrobromic acid, sulfuric acid andphosphoric acid.
 3. A process according to claim 1, wherein either R¹ orR² in the formula (III) represents a hydrogen atom and said acid isprovided in an aqueous solution of not more than 5% by weight of aceticacid or in an aqueous solution of not more than 0.1% by weight of amember selected from the group consisting of hydrochloric acid,hydrobromic acid, sulfuric acid and phosphoric acid.
 4. A processaccording to claim 1, wherein none of R¹ and R² in the formula (III)represents a hydrogen atom and said acid is provided in an aqueoussolution of not more than 20% by weight of acetic acid or in an aqueoussolution of not more than 1% by weight of a member selected from thegroup consisting of hydrochloric acid, hydrobromic acid, sulfuric acidand phosphoric acid.